Additives for lubricants



Patented July 9 1946 2403.894 ADDITIVES roe LUBRICANTS John D.Bartleson, Cleveland, Ohio, assignor to The Standard Oil Company,Cleveland, Ohio, a corporation of Ohio No Drawing. Application June23,1945,

Serial No. 601,321

19 Claims. (01. 252-32.?)

This invention relates to lubricants and lubricant additives suitablefor use under various conditions, including high temperatures or highpressures or both, as for instance, use in an internal combustion engineoperating at higher temperatures and in-which the lubricant is in closecontact with metallic surfaces, metal compounds and high temperaturegases, and use as gear lubricants when surfaces must be lubricated whichare subjected to high pressures.

ihis application is a continuation-in-part of application Ser. No.558,079, filed October 10, 1944.

It is an object of the present invention to provide an agent which maybe useful itself as a lubricant, and which when added to lubricants willmarkedly inhibit the very objectionable deposition of lacquer. and, atthe same time, inhibit acid and sludge formation, corrosion and othertypes of deterioration occurring under operating conditions.

A further object is the provision of lubricating oils containing such anaddition agent.

Another object of this invention is. to provide an agent which whenadded to lubricants will improve the extreme pressure characteristicsthereof. 1

Another object of this invention is to provide heretofore unknowncompositions made from raw materials not heretofore used in makingproducts of this type, together with processes for their production.

Another object is to provide a novel composition which is superior inits functions to other compositions now available and intended for thissame general purpose.

Other objects of this invention will be apparent as it is more fullydisclosed hereinafter. All these objects are achieved in accordance withthe more detailed description of the invention hereinafter.

It has been proposed heretofore to react PCla. P0013, and PSCla withvarious amines In this proposal the temperatures used are relativelylow,

i. e., a maximum of 240 to 265 F. The art has suggested, contrary tofact, that P285 might be the equivalent of the above halogenatedcompounds. We have found that when PaSs is reacted with an amine havingat least twelve carbon atoms, and under the above conditions, theproducts are difiicultly soluble in oil. We have also noted that duringsuch a reaction no gaseous byproducts are evolved.

It has now been found, and unexpectedly indeed, that if a phosphorussulfide-amine reaction is conducted at a sufliciently high temperature,the reaction product will have a high solubility in 2 lubricating oilsand greases and that such products have highly advantageous propertiesas additives for lubricants. Alternatively, the reaction product may bemade at a lower temperature and subsequently subjected to the hightemperature. These products are particularly valuable as additives forso-called extreme pressure lubricants, and also as additives forlubricating oils to im prove the corrosion, lacquer, sludge, viscosityincrease, and the like characteristics thereof. In addition, if anelement of the sulfur family, i. e., sulfur, selenium or tellurium, isincorporated into the product while or preferably after the products aresubjected to the high temperature, still further improved additives areobtained. The metal derivatives formed from all of these sulij lde-aminederived products also have these desired properties.

A method of preparing metal derivatives of the phosphorus sulfide-aminereaction products having the above properties is to prepare thephosphorus sulfide-amine reaction product under temperature conditionsother than the hightemperature and then to prepare the metal derivativethereof under the high temperature conditions. Where thehigh'temperature condition is employed in the primary sulfide-aminereaction step, the step of forming the metal derivative may be conductedunder temperature conditions other than the high temperature.

The high temperature conditions vary somewhat with the amine used, butin general the temperature must be at least about 400 F., and desirablyin the range of about 430 to 530 F. and preferably about 500 F. atatmospheric pressure. Economy of 'heat suggests that a temperaturehigher than that necessary to carry out the reaction will be wasteful.The temperature should not be so high as to decompose the reactionproduct, and 600 F. may be viewed as a practical economic upper limit,although much higher temperatures produce a satisfactory product. Thereaction time varies somewhat with the amine and the temperature andfalls within the general range of from 1 minute to about 6 hours,

desirably from about A to about hour and preferably about A; hour. Thereaction is somewhat exothermic and on a commercial scale the heatevolved thereby may be used to maintain the temperature. The ingredientsmay be added in increments if this is desirable for temperature controlor for'other reasons.

The reactions may be carried out in the ab sence of air or in anatmosphere of an inert gas. such as nitrogen.

e 3 The sulfide-amine reaction may be carried out with direct admixtureof the reactants, or by their admixture in the presence of a diluentwhich erties as that to which the new composition is to be added, may beused as a diluent which is not to be removed. In a commercial embodimentof the invention, a diluent probably would ot be The reaction isusually. complete in four hours or less time. The reaction time is afuncticnof the temperature, the amount of the sulfide'that is to react,the subdivision of the sulfide, rate of stirring, etc.

The amine or mixture of amines may be reacted with the sulfide ormixture of sulfides in moi ratios of one moi of amine tots-om 0.5 to 2:5or more mols oi sulfide. The unexpectedly large amount of the sulfidewhich can be consumed in the reaction is believed to. unique in filehigh temperature reaction. Even smail amounts show a significantimprovement. noruic factors may make it undesirable :to use more thanabout 2.5 mols oi the sulfide. erally about 0.7 to 2.2 mols is the usualrange will be used, and about 1.0 to about '15 is especially desirable.

Y which is a hydrogen attached directly to the ni trogen. The choice maybe controlled the do lubricant solubility characteris primarysulfide-amine or the finalv tive product. Primary and sec amines whichhave an. alip-haticsradical of? at least twelve carbon atoms arepreferred, and these the monoor di-octadecyl or hexadecyl amines ormixtures containing at least one of them. aregiven as illustrative.Analogous poly-' amines may be used. Commercial dioctadecyh amine is acommercially available amine and for this reason is used in. many of theillustrative examples.

The amine stock ma be a mixture of different amines of differentmolecular weight and degrees of substitution. Tertiary amines, althoughnot as desirable, may be present. Generally, the more saturated aminesare preferred.

The yield is very high and appreciable amounts of oil insoluble productsare not formed. Generally the amount of sulfide is chosen so that itwill all react at the temperature selected, and the reaction iscontinued until it is consumed. Associated with the high temperaturetreatment.

alinstir,

such as sodium, potassium and lithium; al

is the evolution of sulfur containing gas, for instance ms.

To achieve the additional improvement which results if additional sulfuris present in the additive, about 0.01 to 2.0 and preferably 0.1 to 0..gram atoms of sulfur per gram mol of the amine is desirable. This sulfurcan be incorporated by adding elemental sulfur, preferably after theformation and cooling of the high temperature primary reaction product,and maintaining the mass at about 200 to 300 F. for about a few minutesto several hours, and preferably about one hour. Selenium and telluriumfunction in much the same way as sulfur in this respect, and may beincorporated similarly. The sulfur can also be ,added to the metalderivatives.

- The" sulfide-amine reaction products may be converted to their metalderivatives by reaction with one or more metal compounds, such as'theirsulfides, oxides or hydroxides. These metals may be one or more of thefollowing: an alkali m line earth metal, such as calcium, barium, strumtium; or aluminum or other metal lower than aluminum in theelectromotive series, such as Zinc, lead, chromium, cob-alt, antimony,tin, copper or molybdenum. The metal should be selected with referenceto the use of the a position and the properties desired in it. alkaliand alkaline earth metals have era-c detergent characteristics. The hevier have surface corrosion inhibition charact The preferred metals aregroup II and groi metals of the periodic table such as zinc, andaluminum.

oduct was made at or heat atures, as des 'oed here ore, the

about 180 to 250 F. being preferred. tion is also usually ccnipieted inhours or less time, and the same factors as to reaction time areinvolved disco" ternatively, i the primeproduct has peratures, the rpared at or sub"- es described as described her but is not filluei cc 1%on, it can be ca over into this step and he s quently separated ifdesired. From about about 6:5) equivalents of the metal compoi may beused per mol of the sulfide in the sulfide-- no reaction product,preferably about 1.0 to about 3.0 equivalents. An equivalent is thequotient of a mol divided by the valence of the metal concerned. Themetal hydroxide is generally insoluble in the sulfide-amine reactionproduct and the amount that reacts is the amount that is no longerpresent as a solid phase in the reaction mass.

It is beneficial to'shave water present in the latter reaction, and thismay be introduced as water of crystallization, or as a hydrate of themetal compound, or it may be introduced separately. A plurality ofmetals can be used such as sodium and calcium, calcium and bariummalciumor zinc and aluminum or'tin. If the amount of the metal is small, thefinal product may be a mixture of the initial reaction product and themetal derivative. The yield in this second reaction is also very high.In the case of the barium compound, the yield is from 90 to 95%, andinthe case of the potassium compound, the yield is almost 100%.

After the reaction is complete, the reaction mass is centrifuged orfiltered to remove water and any traces of oil-insoluble by-productsubstances. If an excess of the basic metal compound is used, theunreacted excess may be separated at this stage. If a volatile solventis used as a diluent, it may be removed by vacuum distillation at thisstage.

. These new compositions impart many desirable properties to lubricantsto which they have been added. They act as very powerful detergents.

oils have more of a. tendency to corrode metals,

orto form acids, sludges and lacquer deposits than others, and such oilsrequire larger quantitles of the addition agent. Also oils that areintended for higher temperatures require larger amounts of the additive.In general, for lubricating oils the range is from 1 to 10% by weightbut under some circumstances amounts as low as -.01% show a significantimprovement. For extreme pressure lubricants the range is from 0.5 to25.0% by weight. As to an upper limit, of course, it may be uneconomicalto add more than is necessary to impart to the lubricant the desiredproperties. Generally, not over about 50% would usually be used.

The following examples of the preparation of new compositions inaccordance with the invention and tables of results of tests oflubricants comprising some of such compositions will serve to illustrateand point out some advantages but in no wise to limit the scope of theinvention as otherwise disclosed and claimed herein.

Example 1 200 grams of phosphorus pentasulfide and 695 grams of No. 300red on (a conventional acid treated Mid-Continent lubricating oil basestock, S. A. E. or slightly lower) were mixed, and heated to 500 F. andmaintained at this temperature for 30 minutes, all in an atmosphere ofnitrogen and with agitation. As it was being heated between 420 and 498F., a considerable amount of gas which largely consisted of H28 wasevolved by the mixture. The reaction mass was then filtered hot. 1443grams of dark oily product was obtained. It was an about 50 weight percent concentrate of the additive in the red oil. It analyzed 5.46%sulfur and 3.58% phosphorus, based on the concentrate.

Example 2 grams of mono-octadecylamine (C. P., analyzing 99% in purity},56 grams of phosphorus pentasulfide, and 455 grams of No. 300 red oilwere mixed, slowly heated to 500 F. and maintained at that temperaturefor 30 minutes, all in an atmosphere of nitrogen and with agitation. Theweight loss during the reaction was 22 grams. Most of this was probablydue to the H28 evolved during the reaction. The reaction mass wasfiltered hot. 54 grams of a brown insoluble material remained as aprecipitate and 471 grams of a liquid product was obtained. The latterwas an about 9 weight per cent concentrate of the additive in the redoil. The liquid-product analyzed 4.90 weight'per cent sulfur and 2.00%'

phosphorus.

Example 3 60.3 grams 'of mono-octadecylamine (C. P.,-

analyzing 99% in purity), 74 grams of phosphorus pentasulflde and 182grams of No. 225

red oil (a conventional acid treated Mid-Continent lubricating oil basestock, of S. A. E. 20) were mixed, slowly heated to 500 F., andmaintained at this temperature for 30 minutes, all

while in an atmosphere of nitrogen, and with agitation. The reactionmass wa then filtered hot..

Amount of phosphorus pentasulflde in grams Example No.

3$$$$$ baseman-a Example Y 10 (a) 1200 grams of commercialdioctadecylamine, 306 grams of phosphorus pentasulfide, 1800 grams ofNo, 225 red oil and 1800 grams of tation for four hours at 300 F.

mass heated with agitation for an additional two hours at 300 F.

(b) 250 grams of the above reaction mass and 31 grams of barium oxidewere mixed and heated for six hours at 500 .F., with agitation. Thereaction mass was filtered hot. grams of filteredproduct wa obtained. Itanalyzed 4.45% ash.

(c) 250 grams of the reaction mass of part (a) above and 34.2 grams ofbarium sulfide were heated with agitation for six hours at 500 F. Thereaction mass was filtered hot. 218 grams of filtered product wasobtained. It analyzed 0.38% ash.

(cc) The above procedure (0) was repeated except that the reaction wascarried out at a temperature of 670 F. for 30 minutes in an atmos phereof nitrogen. 1

Example 11 (a) 800 grams of commercial dioctadecylamine, 281 grams ofphosphorus pentasulfide,

1200 grams of No, 225 red oil and 1200 grams of v 7 gen and withagitation. The reaction mass was cooled to 300 F. 12.1 grams of sulfurwas added and the mass maintained at 800 F. with agitation for one hour.The reaction mass was filtered hot. 3414 grams of dark oily product wasobtained. It analyzed 4.67% sulfur and 2.26%

phosphorus. 1

(ca) The above procedure was repeated except that 16.0 instead of 12.1grams of sulfur was added. 1

(aaa) The above procedure was repeated except that 24.2 instead of 12.1grams of sulfur was added.

(5) 3365 grams of the above filtered reaction product. (a) and 4'79grams of barium hydroxide octahydrate Were mixed and heated withagitationflat 190 F. for three hours. The reaction mass was blown withair while maintained at 200 F. for six hours and then while maintainedat 250 Flor three hours. It was filtered hot. 3420 grams of a filteredhomogeneous dark oily product was obtained. It was an about 25 weightper cent concentrate or solution of the additive in the red oil mixture.The concentrate analyzed 9.71% ash, 5.60% barium, 2.75% sulfur and 2.25%phosphorus.

(bb) The procedure of (b) above was repeated except that the reactionproduct (aa) was used.

(bbb) The procedure of (b) above was repeated except that the reactionproduct (aaa) was used. 1

Example 12 v 800 grams of commercial dioctadecylamine, 205 grams ofphosphorus pentasulfide, 1200 grams of No. 225 red oil and 1200 grams ofNo. 300 red oil were mixed, slowly heated to 500 F. and maintained atthis temperature with agitation for 30 minutes, all while in anatmosphere of nitrogen and with agitation. 695 grams of barium hydroxideoctahydrate was then gradually added over a period of six hours whilethe reaction mass was agitated and maintained at this temperature. Thereaction mass was then blown with air while maintained at 200 F. for sixhours. The reaction mass was filtered hot. 4000 grams of a filteredliquid product was obtained. It was an about 25 weight per centconcentrate of the additive in the red oil mixture. The concentrateanalyzed 7.92% ash, 4.66% barium, 2.40% sulfur and 1.56% phosphorus.

Following the procedure of Exampl 12, metal derivative products wereprepared by varying the amounts of the reactants, as follows:

Amounts in grams of-- Example No. Commercial dioctadecylamine Phosphoruspentasulfide Barium octahydrate products of the invention, as additivesto improve the extreme pressure characteristics of -lubrl-.

cants, compositions of standard Mid-Continent acid treated lubricatingoil base stock. blended with a Mid-Continent bright stock made up with.

the products of Examples 1, 2 and 3 showed the following Values ofPressure wear index .on the Shell four ball tester.

. In order to demonstrate the properties of the metal derivatives of thenew phosphorus sulfideamine reaction products and their metalderivatives in improvin the characteristics of lubricating oils, a largenumber of representative additives were incorporated into conventionallubricating oils. The lubricating oils containing these 1 additives weretested according to laboratory test procedures for evaluating theservice stability of oils as described in a paper by R. E. Burk, E. C.Hughes, W. E. Scovill and J. D. Bartleson presented at the ,AtlanticCity meeting of the American Chemical Society in September, 1941, and inanother paper by the. same authors presented at the New York citymeeting of the American Chemical Society in September, 1944, publishedin: Industrial and Engineering Chemistry, Analytical edition, vol. 1'7,No, -5, May, 194.5, pages 302-309. The latter paper also correlates theresults of such laboratory tests with the so-callecl standardizedChevrolet engine test.

Essentially the laboratory test equipment con sists .of a vertical,thermostatically heated, large glass test tube, into which is placed apiece of steel tubing of about one third its length and of much smallerdiameter. A piece of copper-lead bearing strip is suspended within andfrom the upper end of the steel tube by a copper pin, and

an air inlet is provided for admitting air into i the lower end of thesteel tube in such a way that in rising the air will cause the oilpresent to circulate. The test tube is filled with an amount of the oilto be tested which is at least suificient to submerge the metals.

The ratios of surface active metals to the volume of oil in an internalcombustion test engine are nearly quantitatively duplicated in the testequipment. In the Standard. test the temperature used is approximatelythe average temperature of the crankcase. The rate of airflow per volumeof oil is adjusted to the same as the average for a test engine inoperation. Of the catalytic efiects those" due to iron are the mostimportant. They are empirically duplicated by the addition of a solubleiron salt. Those due to leadbromide are duplicated by its addition. Inthe Standard test, 0.012% of iron salt is added; and in the Irontolerance test this is increased to 0.05%. The duration of the test isadjusted to that usually used in engine type tests. As is shown by thedata in the papers referred to, the laboratory tests have beencorrelated with engine tests and the properties of the oil in an enginemay be determined from the result of the laboratory tests. Y

9 The results given in the following tables were obtained from testsusing:

The "Iron tolerance tests were run at 280 F. for 36 hours. The lacqueris deposited on the steel tube and is determined by'difference in weightof the tube after washing with chloroform and drying to constant weight.The oil insoluble sludge remaining in the glass tube is thought to berelated to similar sludge deposits in engines, and was rated visuallyagainst color photographic standards, an appearance rating scale rangingfrom F (worst) through A (best) being used. The corrosion was determinedby difference in weight of the copper and heavy metal pieces afterscrubbing with chloroform. The used oil was sufiicient to enable thedetermination of all of the usual oil tests, viz. isopentane insolubles,viscosity, acid number, etc. The data in the following tables shows thresults obtained in testing ournew additives by the tests described.Iron tolerance tests on a conventional Mid- Continent acid treatedlubricating oil base stock blended with Mid-Continent bright stock (S.A. E. 30), and compositions containing this oil and a high temperaturephosphorus pentasulfide amine reaction product or metal derivativethereof were run on a number of the additives; the results given in thefollowing tables are representative:

Table I Additive from Example No None 1 2 3 Concentration of additive inper cent by weight None 1. 5 1. 6 1. 5 Lacquer deposit (in milligrams)l9. 3 0. 3 0.4 12. 0 Sludge (isopentane insoluble in milligrams 21. 913.4 88. 5 Corrosion (in milligrams) weight loss 2. 3 1. 2 37. 7 15. l5.2 0. 9 -6. 8 '-1. 7 8. 2 l. l 6. 5 2.9 Viscosity increase (SUS) 1, 05178 98 40 Appearance rating F A 13+ 0 These data show the markedimprovement imparted to the lubricating oil by the high temperaturephosphorus sulfide-amine reaction products of the invention in everyindicated characteristic but one. Example 1 shows a product optimum foruse in an internal combustion engine where E. P. properties are notrequired. Example 3 shows that reasonably good properties can beobtained with the use of a very small amount of the sulfide. When E. P.properties are wanted, and where copper corrosion is not a factor,Example 2 is excellent. Where copper corrosion is a problem, theaddition of sulfur as disclosed hereinbefore, results in improvement ofthis characteristic also, as shown in Table III hereinafter.

Table II (A) Table I I (B) Additive from Exam le No None 7 8 9Concentration oi ad itive in per cent by we None 1. 5 1.5 1.5 Lacquerdeposit (in milligrams)- l9. 3 0. l 2. l 2. 1 Sludge (isopentaneinsoluble in millia grams 5.5 43.8 101.5 Corrosion (in milligrams)weight loss of:

15. 8 0.0 61.8 1. 3 l. 9 1. 4 2. 4 3. 4 3. 0 e7 81 Appearance rating AB- B- The data of Tables II(A) and II(B) show the improved lubricantproperties imparted by phosphorus sulfide-amine additives of theinvention of a wide range of ratios of phosphorus sulfide to the amine.The products of Examples 5 and 6 show marked improvement in everyindicated characteristic. As stated hereinbefore, the copper corrosioncharacteristic of the other additives in these tables can be improved byincorporation of sulfur if desired.

Table III Additive from Example No--- None 11(a) 11(aa) 11(41) 11(aa)Concentration of additive in per cent by weight None 1. 0 1. 0 1. 5 l. 6Lacquer deposit (in milligrams). l9. 3 l. 0 0. 6 0. 9 0. 5 Sludge(isopentane insoluble in milligrams) 4. 5 43. 6 6. 5 8. 1 Corrosion (inmilligrams) weight loss of:

Copper 2. 3 1. 7 0. 3 l. 6 -0. 1 Copper-lead 5. 2 0. 3 l. 1 0. 8 1. 0Acid number. 8. 2 0. 9 l. 0 1. 0 1. 1 Viscosity increase. 1,051 33 50 3338 Appearance rating F A+ A+ A+- A+ These data show the markedimprovements in every indicated characteristic imparted to the oil bythe high temperature phosphorus sulfideamine reaction productsof'theinvention containing added sulfur. They also show that amounts of 1.0%of the additive are very effective.

Table IV Additive from Example p No None 10(b) 10 (c) 10(cc) 11(6) 12Concentration of additive in per cent by weight... None l. 5 1. 5 l. 53. 0 4.0 Lacquer deposit (in milligrams) 19.3 0.3 i 1.3 8.0 0.0 0.4Sludge (isopentane insoluble in milligrams). 823.7 197.4 281.2 1.1 0.9Corrosion (in milligrams) weight loss of:

Copp 2.3 1.3 0.1 1.6 1.0 0.9 Copper-lead 5. 2 72. 9 2. 8 2. l 0. 1 -0. 3Acid number 8. 2 3. 4 1. 5 4. 4 l. 2 0.9 Viscosity increase 1. 051 17084 253 47 39 Appearance rating F A A C A A These data show thesubstantial improvements imparted to the lubricating oil by the metalderivativ high temperature products of the invention. It is noteworthythat the barium sulfide .derived product is distinctly superior to .the

corresponding barium oxide derived produced 10b Table V Additive fromExample No None 131 14 Concentration of additive in percent by 'WOlEl'lLNone 7 1. .5 4. Lacquer deposit (in milligrams) l9.- 3 0. 0 0. Sludge(isopentane insoluble in milligrams) 828. 7 94. 1 0. Corrosion (inmilligrams) weight ss oi:

Appearance rating These data show the phenomenal improvements impartedto lubricants in every indicated charac- 11 teristic by the metalderivative additives of the invention, especially when used in 4%concentration. The use of a 1.5% concentration gives The standardizedChevrolet engine testf fgr testing lubricating oils, referred topreviously,

is relatively slow and expensive. New piston rings and two newcopper-lead bearing inserts are installed in the motor prior to eachtest. The labbratory test discussed hereinbefore is preferred where testdata are wanted for a large number of samples. 7

In the Chevrolet engine test, the engine is a conventional Chevroletengine with 216.5 cu. in. piston displacement and a compression ratio of6.5 to 1. Prior to each test new piston rings and "two new copper-leadbearing inserts are installed.

the power section, and properties of the used oil,

sampled near the middle and also at the end of the test, are examined.

The test is primarily a corrosion test and corrosion standards of theart are associated with this test. A weight loss, from corrosion, ofabout 350 mgms. per bearing is acceptable but of course alower weightloss is more desirable.

Although the laboratory test is the more practical way of testing alarge number of samples in a relatively short time, engine tests weremade on some of the additives of the invention. The added-sulfur metalderivative additives of Example 11 showed particularly desirable lowcorrosion characteristics. All the other characteristics tested werewell within accepted values. The following Chevrolet test data areillustrative of corrosion characteristics of a Mid-Continent S. A. E. 30oil containing 3% of the additive.

Example No. 1

11b llbb llbbb Added sulfur (gm. atoms S/gm.

in amino) 0. 33 0.44 0.66 Corrosion (weight loss in mgmsJ bearing) 256158 382 The intermediate sample Ex. llbb is by far the best, the loweradded sulfur sample Ex. 11b is well within the accepted standard. Thislow corrosion value, accompanied by all of the other desirablecharacteristics of the additives of the invention is indeed striking.Low corrosion is an important property in an addititve. It is not alwaysobtained since additives which give other desirable properties oftenincrease corrosion. Because of the diverse factors involved in achievinglow insolubles, low lacquer, low viscosity increase, low corrosion,etc., it is very dificult to produce an additive which is nearly optimumfor all factors, especially corrosion. The upper sample Ex. llbbb is notwithin the 350 mgms/bear- 12 when sulfur is to be added, a range ofabout 0.25 to about 0.64 gram atomsof sulfur per gram mol of amine inthe additive is preferred, for the above standard.

In order to prevent foaming of the oil containing a small proportion of,the additive it is desiring standard. The latter is suitable for usewhere corrosion is not a major factor. By plotting the above data anddrawing a smooth curve through the three points, it is determined that,

able in some cases to add a very small amount of tetra-amyl silicate, oran alkyl ortho carbonate, ortho formate or ortho acetate. 0.000370 ofpolyalkyl-silicone oil, or 0.001% of tetra-amyl silicate was found toprevent foaming upon bubbling of air through oil containing a few percent of the additive.

It will be obvious to one skilled in the art that sulfide-amine reactionproducts and similar products obtained by introducing phosphorus.

and/or sulfur into an amine as prepared according to differentprocedures but having substantially the same properties as those hereindescribed, may be converted to metal derivatives or made-up intolubricant compositions or both in accordance with the invention. Theinvention as claimed contemplates such compositions as set forth in thefollowing claims.

Iclaim:

1. A- lubricant comprising an oil dispersible reaction product of anorganic amine and a phosphorous sulfide subjected to a temperature ofabove about 400 F. and below temperatures at which the reaction productwould be decomposed.

2. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible reaction product of anorganic amine and a phosphorus. pentasulfide reacted at a temperature ofabove about 400 F. and below temperatures at which the reaction productwould be decomposed.

3. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible reaction product of anorganic amine and a phosphorus sulfide subjected to a temperature ofabove about 400.F. and below temperatures at which the reactionproduct'would be decomposed, and which contains an added element of thesulfur family in chemical combination.

4. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil. dispersible metal derivative of areaction product of an organic amine and a phosphorus sulfide subjectedto a temperature of above about 400 1 and below temperatures at whichthe reaction product would. be decomposed.

5. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible metal derivative of areaction product of n or nic amine and phosphorus pentasulfide subjectedto a, temperature of above v 12 carbon atoms subjected to a temperatureof above about 400 F. and not over about 600 F.

7. An additive for lubricating Oils and greases to improve theircharacteristics, comprisin an oil dispersible reaction product ofphosphorus pentasulfide and an organic amine having at least one aminohydrogen and. a radical of at least 12 carbon atoms subjected to atemperature of above 13 about 400 F. and not over about 600 F. and whichcontains added sulfur in chemical combination.

8 An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible metal derivative of areaction product of phosphorus pentasulfide and an organic amine havingat least one amine hydrogen and a radical of at least 12 carbon atomssubjected to a temperature of above about 400 F. and not over about 600F.

9. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible metal derivative of areaction product of phosphorus pentasulfide and an organic amine havingat least one amine hydrogen and a straight chain radical of at least 12carbon atoms subjected to a temperature of above about 400 F. and notover about 600 F. and which contains added sulfur in chemicalcombination.

10. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible reaction product of onemol of an organic aminehaving at least one amine hydrogen and a radicalof at least 12 carbon atoms and at least about 0.5 mols of phosphoruspentasulfide subjected to a temperature of above about 400 F. and notover about 600 F.

11. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible reaction product of onemol of an organic amine having at least one amine hydrogen and a radicalof at least 12 carbon atoms and at least about 0.5 mols of phosphoruspentan sulfide subjected to a temperature of above about 400 F. and notover about 600 F. and which contains about 0.01 to 2.0 gram atoms addedsulfu in chemical combination.

12. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible metal derivative of areaction product of one mol of an organic amine having at least oneamine hydrogen and a radical of at least 12 carbon atoms and at leastabout 0.5 mols of phosphorus pentasulfide subjected to a temperature ofabove about 400 F. and'not'over about 600 F. containing 0.25 to about6.0 equivalents of the metal per mol of the sulfide reacted.

13. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible metal derivative of areaction product of one mol of an organic amine having at least oneaminehydrogen and a radical of at least 12 carbon atoms and at leastabout 0.5 mols of phosphorus pentasulfide subjected to a temperature ofabove about 400 F. and not over about 600 F. and which contains about0.01 to 2.0 weight unit atoms added sulfurin chemical combination andcontaining 0.25 to about 6.0 equivalents of the metal per mo1 of. thesulfide.

14. An additive for lubricating oils and greases to improve theircharacteristics, comprising an iii oil dispersible reaction product ofone mol of an octadecylamine having at least one amine hydrogen and atleast about 0.5 mols of phosphorus pentasulfide subjected to atemperature of above about 400 F. and not over about 600 F.

15. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible metal derivative of areaction product of one mol of an octadecylamine having at least oneamine hydrogen and at least about 0.5 mols of phosphorus pentasulfidesubjected to a temperature of above about 400 F. and not over about 600F. and which contains about 0.01 to 2.0 weight unit atoms added sulfurin chemical combination and containing 0.25 to about 6.0 equivalents ofthe metal per mol of the sulfide.

16. An additive for lubricating oils and. greases to improve theircharacteristics, comprising an oil dispersible barium metal derivativeof a reaction product of one mol of a dioctadecylamine and at leastabout 0.5 mols of phosphorus pentasulfide subjected to a temperature ofabove about 400 F. and not over about 600 F. containing 0.25 to about6.0 equivalents of the metal per mol of the sulfide.

17. An additive for lubricating oils and greases to improve theircharacteristics, comprising an oil dispersible reaction product of onemolof diactadecylamine and at least about 0.5 mols of phosphoruspentasulfide subjected to a temperature of above about 400 F. and notover about 600 F. and which contains about 0.01 to 2.0 weight unit atomsadded sulfur, said reaction product having been subjected after additionof added sulfur to a temperature of at least about 200 F. and not overabout 600 F. for at least about a few minutes.

18. A lubricant comprising a, mineral lubricating oil and from 0.05 to10.0 weight percent of an oil dispersible reaction product of one mol ofa dioctadecylamine and at least about 0.5 mols of phosphoruspentasulfide subjected to a. temperature of about 500 F. and whichcontains about 0.01 to 2.0 gram atoms added sulfur, said reactionproduct havin been subjected after addition of added sulfur to atemperature of at least about 200 F. and not over about 500 F. for atleast about a few minutes.

19. A lubricant comprising a mineral lubricating oil and from 0.05 to10.0 weight percent of an oil dispersible barium metal derivative of areaction product of one mol of dioctadecylamine and at least about 0.5mols of phosphorus pentasulfide subjected to a temperature of about 500F. and which contains about 0.25 to about 6.0 equivalents-of the metalper mol of the sulfide and about 0.01 to 2.0 gram atoms added sulfur,said reaction product having been subjected after addition of addedsulfur to a temperature of at least about 200 F. and not over about 500F. for at least about a few minutes.

JOHN D. BARTLESQN.

